Dyestuffs of the anthrapyrimidine series



DYESTUFFS OF THE SERIES FrankLodg'e and. James Wardleworth,Blackley,,Man-

chester, England, assignors' to Imperial Chemical 1ndustries Limited, acorporation of'Great Britain No; Drawing. Application October .18,195.4,. Serial No. 463,026

Claims priority, application Great Britain October 21-, 1953 6 Claims.(Cl.1 260.261);

This invention relates to new dyestulfs and more par- 1 ticularly to newacid dyestuffs of the anthrapyrimidine series.

The anthrapyrimidines referred to in this specification are2-aryl-1':9-anthrapyrimidines, that is to say those compounds whichcontain in their structure the grouping -N=CArN=, Where Ar is an arylnucleus, connected to the 1' and 9' carbon atoms of the anthraquinonenucleus to form a pyridinering fused with the anthraquinone residue.

The system of numbering used for anthrapyrimidine derivatives in thisspecification is that given .for the parent ring systemin TheRingIndex,1940, by Patterson and .Capell, publishedby the Rheinhold PublishingCorporation, page362, No. 2676.

In .German specification No. 633,599 a process is de- :1

scribed for the manufacture, of wooldyestuffs by-sulphonating certainantrapyrimidines, including. the6-pto1uidino-2-aryl-1':9-anthrapyrimidines where the and radical isphenyl, a-naphthyl or ,B-naphthyl.

The dyestuifs of this. kind obtained under mild sulphonation conditions,are sparingly soluble in water so thatthey, tend to crystallise .outfrom the dyebath. Furthermore they give dyeings. on Wool which have poorrubbing fastness. The more soluble dyestufis. obtained under more severesulphonation conditions are free from t these disadvantages but theygive dyeings of poor fastness to washing and milling.-

We have now found that byintroducing at least. two sulphonic acid.groups,v into. certain .v6-arylamino-2-aryl- 1':9'anthrapyrimidines ofhigh moleculanweight, there I areobtained scarlet to redacid dyestuffswhich havev good solubility in the ,dyebath and also. give brightscarletto red dyeings on wool of excellent wet fastness properties.

According to our invention We provide new acid dyestufis which in theirfree acid form are represented by' the formula:-

! l O R R 2,778,831 Pa e ted Jan. 22,1957

ice

'stufis which. comprises sulphonating a 6-arylamino-2-aryl-1':9'anthrapyrimidine of the formula; 1

wherein Ar and R havethe significance given above to introduce at least2sulphonic acid groups into the molecule.

The sulphonation may be carried out for example by stirring the,fifarylamino-2-aryl-lz9 -anthrapyrimidine in sulphuric acid or oleum ata suitable temperature until a test portion of the reaction mixture iscompletely soluble in 'warmwaten The product may be isolated by'pouringthe reaction mixture onto about 3 parts by weight of ice, and water,filtering off. the solid product so precipitated stirring thiswith,brine, neutralising .withsodium carbonate and filtering ofi thesodium salt of the dyestuffs.

The starting materials for use in the invention may be made bycondensing the appropriate substituted arylamine with-theappropriate-;6-chloroor 6-bromo-2-ary1-1':9'- anthrapyrimidinewhich-itself may be made by condensing theN-methyl derivative of theappropriate aryl carboxylic acid amide with 1-chloro-, orl-bromo-4-aminoanthraquinone by means-of thionyl chloride in thepresence of an inert diluent.

Suitable starting materials are for example6-p-cyclohexylanilino-2-p-phenylphenyll 9-anthrapyrimidine, v 6-p-n-octylanilino-2-p-phenylphenyl-1' 9'- anthrapyrimidine, 6-(artetrahydro-B-naphthylamino)-2 p phenylphenyl- 1':9'anthrapyrimidine,-p-n-butylanilino 2 p phenylphenyl-l':9-anthrapyrimidine and thecorresponding Z-pphenoXyphenyl-, -2-u-naphthyland -2- 8-naphthylcompounds.

The dyestufis made by the process of our invention are normally isolatedin the form of their salts, especiallythe alkali metal salts. They havegood solubility in the dyebath and dye wool in bright scarlet to redshades of very good fastness to washing, milling, perspiration andlight.

The invention is illustrated but not limited by the following examplesin whichthe parts are by weight:

Example 1 20 parts of 6-p-n-butylanilino-2-p-phenylphenyl 1':9'anthrapyrimidine (red crystals, melting point 203-204 C., which may beobtained by condensing p-n-butylaniline with 6-chloroor 6-bromo-2-p-phenylphenyl-l:9-anthrapyrimidine) are dissolved-with stirring in 280parts of sulphuric acid at 20 C. 192- parts of oleum containing 20% offree sulphur trioxide are added, and the solution is stirred at 20 C.until a test portion of the solution is completely solublein water at 35C. This requires about 1 hour. The solution is poured onto 1500 parts ofice and water, and the solid product is filtered oif and mixed with 10%brine. Sutficient sodium carbonate is added to make the suspensionalkaline and the dyestutf is then filtered oil from the red suspension,washed on the filter with 10% brine and dried.

The product which is essentially the sodium salt of a disulphonic acid,dissolves in cold water to give a reddish-orange solution, and dyes woolfrom neutral or weakly acid dyebaths in bright scarlet shades ofexcellent fastness to wet treatments.

ExampleZ 20 parts of6-p-n-butylanilino-2-p-naphthyl-1':9-anthr'apyri'midine (orangecrystals, melting point 212-2l3 C. which may be obtained by condensingp=n u'tylanil'in'e' Example 3 20 parts of6-p-n-butylanilino-2-pphenoxyphenyl- 1':9'-anthrapyrimidine (redcrystals, melting point 158-159 C. which maybe made by condensingp-nbutylanilin e with 6-chloro-, or6-bromo-2-p-phe'noxyphenyl-l':9'-anthrapyrimidine) are dissolved in 370parts at 100 sulphuric acid at 10 C. 96 parts of oleum containing 20% offree sulphur trioxide, are added and the solution is stirred at 10C.until a test portion of the solution is completely soluble in water at35 C. The dyestufi is isolated a's described in Example 1. The reddyestufi so obtained is soluble in cold water to give a reddish-orangesolution, which dyes" Wool from neutral or weakly acid dyebaths inbright scarlet shades of very good fastness to wet treatments.

Example 4 20 parts of 6-p-cyclohexylanilino-2-pphenylphenyl- 1:9-anthrapyrimidine (red crystals, melting point 204-205 C., which maybe obtained by condensing pcyclohexylaniline with 6-chloroor6-bromo-2-p-phenylphenyl-I':9-anthrapyrimidine) are dissolved withstirring in 280 parts of 100% sulphuric acid at 20 C. 100 parts of oleumcontaining 20% of free sulphur trioxide are added and the mixture isstirred at 20 C. for 16 hours, and then poured into 1,500 parts of iceand water. The solid product is filtered E and the dyestufi is isolatedas described in Example 1. The bright red powder so obtained isessentially the sodium salt of a disulphonic acid. It gives a clearscarlet solution in water and dyes wool from neutral or weakly aciddyebaths in bright scarlet shades of very good fastness to washing andlight.

Similar scarlet shade wool dyestuffs may be obtained by sulphonating6-p-n-octylanilino-2-p-phenylphenyl-1':'9 anthrapyrimidine or6-(ar-tetrahydro ,B-naphthylamino)- 2-p-phenylphenyl-1'9'-anthrapyrirnidine.

What we claim is:

1. New acid dyestufis which in their free acid form are represented bythe formula:

wherein Ar represents a member selected from the group consisting ofa-naphthyl fl-naphthyb," p phenylphenyl and p-phenoxyphenyl-radicals, Rrepresents a member selected from the group consisting of an anilineradical carrying in the 4-position a cyclohexyl radical, an anilineradical carrying in the f-posit'ion an alkyl radical containing at least4 and not more than 12 carbon atoms, and an aniline radical carrying onthe 3- and 4-positions a reduced ring, and n is a whole number greaterthan 1 with a sulphonating agent selected from the group consis ting ofsulfuric acid and oleum until the resulting mixture is comgsie tely'soluble in water.

2. The acid dyestufi which in its free acid form is6-p-nbutylanilino-Z-p plienylphenyl 1':9' anthrapyrimidinedisulphonicacid. p I r I p 3. Process for the nianiifaetureof new acid dyestufiswhich comprises sulphonating by treating a 6-arylamino-2-ary1-1':9'-anthrapyrirnidine of the formula:

wherein reni'esents a member selected from thegreu'p consisting ofa-naphthyl'-', fl naphthyl p-phenylp'henyb', and pphno'xyphenyl-i'adicals, R represents a member selected from the groupconsisting of an aniline radical carrying'in the 4-position a cyclohexylradical, an aniline radical carrying in the 4-position an alkyl radicalcontaining at least 4 and not more than 12 carbon atoms, and an anilineradical carrying on the 3- and 4-po'sitions a reduced ring, and n is awhole number greater than 1 with a sulphonating agent selected from thegroup consisting of sulfuric acid and oleum until the resulting mixtureis' completely soluble in water to introduce at least 2 sulphonic acidgroups into the molecule.

4. The acid dyestuff which in its free acid form is represented by theformula of claim 1 wherein Ar is (B-naphthyl and R is p-n-butylanilino).

5. The acid dyestufr' which in its free acid form is represented by theformula of claim lwherein A1 is 2- p-ph'enoxyphenyl and R isp-n-butylanilin'o.

'6. The acid dyestufi which in its free acid form is represented by theformula of claim 1 wherein A1- is 2- phehylphenyl and R isp-cyclohexylanilino.

References Cited in the file of this patent UNITED STATES PATENTS

1. NEW ACID DYESTUFFS WHICH IN THEIR FREE ACID FORM ARE REPRESENTED BYTHE FORMULA: